The nickel-catalyzed reduction of secondary and tertiary amides to give amine products is reported. The transformation is tolerant of extensive variation with respect to the amide substrate, proceeds in the presence of esters and epimerizable stereocenters, and can be used to achieve the reduction of lactams. Moreover, this methodology provides a simple tactic for accessing medicinally relevant α-deuterated amines.

We report the formation of iminium-trifluoroborates (TIMs) from potassium acyltrifluoroborates (KATs) and the synthesis of α-aminotrifluoroborates and α-aminoboronic acids from TIMs.

Photocatalytic coupling of aldehydes and silicon amine protocol (SLAP) reagents enables the simple, scalable synthesis of substituted morpholines, oxazepanes, thiomorpholines, and thiazepanes under continuous flow conditions. Key to the success of this process is the combination of an inexpensive organic photocatalyst (TPP) and a Lewis acid additive, which form an amine radical cation that is easily reduced to complete the catalytic cycle. Di- and trisubstituted SLAP reagents are formed in one step by an iron-catalyzed aminoetherification of olefins.

We report synthetic studies pertaining to two heterocyclic aryne intermediates: the 2,3-pyridyne and the 4,5-pyrimidyne. First, a 2,3-pyridyne precursor was readily accessed from 2-pyridone using a known procedure. Subsequently, 2,3-pyridyne generation and trapping were used to access several functionalized pyridines in a regioselective manner. In addition, we report synthetic routes to two isomeric silyltriflates, which were intended to serve as precursors to the 4,5-pyrimidyne. Consecutive 4,5-pyrimidyne generation and trapping experiments were ultimately deemed unfruitful. We expect these findings will promote the use of 2,3-pyridyne and other heterocyclic arynes as building blocks for the synthesis of functionalized heterocycles.

The cross-coupling of α-aminoalkyltrifluoroborates and Grignard reagents to form N, N-substituted α-tertiary amines (ATAs) is reported. Key to the success of this reaction is the unexpected oxidation of the α-aminoalkyltrifluoroborate to the corresponding iminium cation by commercially available Barluenga's reagent. Various Grignard reagents added smoothly, enabling the synthesis of a variety of ATAs, which are of high value for medicinal chemistry and drug development. Many of the reported examples are not accessible by the established methods.